Diaminopyrazole derivatives and oxidation hair dyes containing pyrazolone derivatives

Abstract

The object of the invention is an agent for oxidatively dyeing keratin fibers, wherein it contains (a) at least one 4,5-diaminopyrazole derivative of Formula (I), (II) or (III) or its salt with organic or inorganic acids,as well as(b) at least one pyrazol-5-one derivative of the general formula (IV), (V) or (VI), or its salt with organic or inorganic acids,

What is claimed is:  
     
       1. An agent for oxidatively dyeing keratin fibers, said agent comprising a combination of 
       at least one 4,5-diaminopyrazole derivative of formula (I), (II), (III) or a salt thereof with an organic or inorganic acid:                    
       wherein R 1  represents hydrogen, a linear or branched C 2 -C 8  alkyl group, an optionally substituted phenyl group or a linear or branched C 2 -C 4  hydroxyalkyl group; 
       R 2  represen hydrogen, a linear or branched C 1 -C 8  alkyl group, an optionally substituted phenyl group or a linear or branched C 2 -C 4  hydroxyalkyl group; 
       R 3  represents a halogen atom, a linear or branched C 1 -C 4  alkyl group or a linear or branched C 1 -C 4  alkoxy group and R 4  represents hydrogen, a linear or branched C 1 -C 4  alkyl group or a linear or branched C 2 -C 4  hydroxyalkyl group; 
       R 5  represents hydrogen, a linear or branched C 1 -C 8  alkyl group, a C 1 -C 4  hydroxyalkyl group, a C 1 -C 4  aminoalkyl group, a C 1 -C 8  alkylamino group, a di(C 1 -C 8 )alkylamino group, a C 1 -C 4  alkylamino-(C 1 -C 4 )alkyl group or a di(C 1 -C 4 )alkylamino-(C 1 -C 4 )alkyl group, an aryl group or a heteroaryl group; 
       R 6  and R 7  may be the same or different and, independently of each other, each represents hydrogen, a linear or branched C 1 -C 8  alkyl group, an aryl group, a heteroaryl group, a carboxylic acid group, a carboxylic acid ester group, an optionally substituted carboxylic acid amide group, a hydroxy group or a C 1 -C 4  hydroxyalkyl group or R 2  and R 3  jointly form an optionally substituted C 1 -C 8  alkylene group; 
       Z is a C 1 -C 10  alkyl diradical, which is optionally interrupted by a hetero atom, an aromatic diradical or a heteroaromatic diradical, which is optionally condensed with one or two benzene rings and/or substituted by a hydroxy group or a C 1 -C 6  alkyl group, or a diradical of formula—Ar-(Alk) n -Ar—, in which Ar is an optionally substituted aryl or heteroaryl group, Alk is a —CH 2  group and n is a whole number from 0 to 6; and x and y, independently of one another; are equal to 0 or 1; and 
       at least one pyrazol-5-one derivative of formula (IV), (V) or (VI), or a salt thereof with an organic or inorganic acid;                    
       wherein R 8  represents a linear or branched C 1 -C 4  alkyl group, a linear or branched C 1 -C 4  alkoxy group, a linear or branched C 1 -C 4  alkoxy-(C 1 -C 8 )alkyl or a linear or branched C 2 -C 4  hydroxyalkyl group; and 
       R 9  to R 13 , independently of each other, each represents hydrogen, a linear or branched C 1 -C 4  alkyl group, a linear or branched C 2 -C 4  hydroxyalkyl group, a hydroxy group, an amino group, a linear or branched C 1 -C 4  alkoxy group; a linear or branche C 1 -C 4  alkoxy-(C 1 -C 4 )alkyl or a linear or branched C 1 -C 4 -hydroxyalkylamino group. 
     
     
       2. The agent as defined in  claim 1 , wherein said at least one 4,5-diaminopyrazole derivative is selected from the group consisting of 4,5-diamino-1-(4′-methylbenzyl)-pyrazole; 4,5-diamino-1-(3′-methylbenzyl)-pyrazole; 4,5-diamino-1-(2′-methylbenzyl)-pyrazole; 4,5-diamino-1-(2′-hydroxyethyl)-1H-pyrazole; 4,5-diamino-1-benzyl-1H-pyrazole; 4,5-diamino-1-ethyl-1H-pyrazole; 4,5-diamino-1-isopropyl-1H-pyrazole; 4,5-diamino-1-pentyl-1H-pyrazole; 4,5-diamino-1-(4′-methoxybenzyl)-1H-pyrazole; 4,5-diamino-1H-pyrazole; 4,5-diamino-1-(3′-methoxybenzyl)-1H-pyrazole; 4,5-diamino-1-(2′-methoxybenzyl)-1H-pyrazole; 4,5-diamino-1-(4′-chlorobenzyl)-1H-pyrazole; 4,5-diamino-1-(3′-chlorobenzyl)-1H-pyrazole; 4,5-diamino-1-(2′-chlorobenzyl)-1H-pyrazole; 4-amino-5-methylamino-1-(4′-methoxybenzyl)-1H-pyrazole; 4-amino-5-(2′-hydroxymethyl)amino-1-(4′-methoxybenzyl)-1H-pyrazole; 4-amino-5-methylamino-1-(2′-hydroxyethyl)-1H-pyrazole; bis-(4,5-diamino-pyrazole-1-yl)-methane; 1,2-bis-(4,5-diamino-pyrazole-1-yl)-ethane; 1,3-bis-(4,5-diamino-pyrazole-1-yl)-propane; 1,3-bis-(4,5-diamino-3-phenyl-pyrazole-1-yl)-propane; 2,3-bis-(4,5diaminopyrazole-1-yl)-propane-1-ol; N-benzyl-2,3-bis-(4,5-diamino-pyrazole-1-yl)-propionamide; 1,3-bis-(4,5-diaminopyrazole-1-yl)cyolohexane; 1,4-bis-(4,5-diaminopyrazole-1-yl-methyl)-benzene; 1,4-bis-(4,5-diamino-pyrazole-1-yl-methyl)-2,5-dimethoxy-benzene; 1,3-bis-(4,5-diaminopyrazole-1-yl-methyl)-benzene; 2,6-bis-(4,5-diaminopyrazole-1-yl-methyl)-4-methylphenol; 1,2-bis-(4,5-diaminopyrazole-1-yl-methyl)-benzene; 1,2-bis-(4,5-diamino-pyrazole-1-yl-methyl)-4,5-dimethoxybenzene; 2,3-bis-(4,5-diaminopyrazole-1-yl-methyl)-naphthalene; 2,3-bis-(4,5-diaminopyrazole-1-yl-methyl)anthracene; 9,10-bis-(4,5-diamino-pyrazole-1-yl-methyl)anthracene; 4,4′-bis-(4,5-diamino-pyrazole-1-yl-methyl)-biphenyl; 1,2-bis-[4-(4,5-diaminopyrazole-1-yl-methyl)-phenyl]-ethane; 2,5-bis-(4,5-diaminopyrazole-1-yl-methyl)-furan; 2,5-bis-(4,5-diaminopyrazole-1-yl-methyl)-thiophene; 2,8-bis-(4,5-diaminopyrazole-1-yl-methyl)-dibenzothiophene; 4,4′-bis-(4,5-diamino-pyrazole-1-yl-methyl)-[2,2]-bipyridyl and 1,2-bis-[6-(4,5-diaminopyrazole-1-yl-methyl)-pyridine-2-yl]-ethane; or is a salt thereof with an inorganic or organic acid. 
     
     
       3. The agent as defined in  claim 1 , wherein said at least one pyrazolone derivative is selected from the group consisting of 3-amino-1-phenylpyrazole-5-one, 3-methyl-1-phenylpyrazole-5-one, 1,3-dimethylpyrazole-5-one, 3methyl-1-(4-sulfphenyl)-pyrazole-5-one, 3-methyl-1-(2-hydroxyethyl)-pyrazole-5-one and 1-phenylpyrazole-5-one; or is a salt thereof with an inorganic or organic acid. 
     
     
       4. The agent as defined in  claim 1 , containing from 0.005 to 20 percent by weight of said at least one 4,5-diaminopyrazole derivative and from 0.005 to 20 percent weight of said at least one pyrazolone derivative. 
     
     
       5. The agent as defined in  claim 1 , further comprising oxidative dye precursors and/or substantive dyes. 
     
     
       6. The agent as defined in  claim 1 , further comprising developer and coupler substances. 
     
     
       7. The agent as defined in  claim 6 , containing from 0.01 to 20 percent by weight of said developer and coupler substances in each case. 
     
     
       8. The agent as defined in  claim 5 , containing said substantive dyes in an amount of from 0.01 to 10 percent by weight in each case. 
     
     
       9. A ready-for-use oxidation dye mixture having a pH of 3 to 11 and made by mixing the agent as defined in  claim 1  with an oxidizing agent in a weight ratio of 5:1 to 1:3.